Detergent compositions and methods of obtaining them

ABSTRACT

1. A METHOD FOR PRODUCING ALKYL SULFATES AND MIXTURES OF OLEFINIC SULFONATES AND ALSO ORTHODIALKYL BENZENE SULFONATES HAVING DETERGENT AND DIODEGRADABLE PROPERTIES WITH SUPERIOR FOAM STABILITY, WHICH METHOD COMPRISES THE STEPS OF: (A) TREATING NORMAL PARAFFIN HYDROCARBONS HAVING BETWEEN 14 AND 24 CARBONATION CATALYST CHOSEN FROM ISOMERIZING DEHYDROGENATION CATALYST CHOSEN FROM THE GROUP CONSISTING OF: CHROMIUM OXIDE AND POTASSIUM OXIDE, DEPOSITED ON ALUMINA; PLATINUM, LITHIUM AND ARSENIC DEPOSITED ON ALUMINA; AND COPPER, POTASSIUM, AND CHROMIUM DEPOSITED ON ALUMINA; IN THE PRESENCE OF HYDROGEN TO YIELD A SUBSTANTIAL AMOUNT OF OLEFINS AND SATURATED STRAIGHT CHAIN ORTHODIALKYL BENZENE HYDROCARBONS; (B) SEPARATING HYDROGEN AND CRACKING PRODUCTS OF THE SAID NORMAL PARAFFIN HYDROCARBONS FROM THE EFFLUX; (C) SULFATING AT LEAST A PART OF THE OLEFIN HYDROCARBONS RESULTING FROM THE DEHYDROGENATION OF THE NORMAL PARAFFIN HYDROCARBONS BY CONTACT OF THE SAID OLEFIN WITH SULFURIC ACID OF A CONCENTRATION OF MORE THAN 90 PERCENT FOR A PERIOD OF TIME BETWEEN 1 AND 10 MINUTES, AT A TEMPERATURE BELOW 25*C.; (D) NEUTRALIZING THE EFFLUENT OF THE SULFATING STEP BY ADDITION OF AN ALKALINE BASE SELECTED FROM THE GROUP CONSISTING OF ALKALI METL HYDROXIDES AND AMMONIA (E) HYDROLYZING THE PRODUCTS THUS NEUTRALIZED WITH AN ALKALINE BASE SELECTED FROM THE GROUP CONSISTING OF ALKALI METAL HYDROXIDES AND AMMONIA TO CONVERT SULFURIC ESTERS PRESENT IN THE PRODUCTS FROM THE PRODUCTS FROM THE SULFATING STEP TO SULFATES WHEREIN AN ORGANIC PHASE AND AN AQUEOUS PHASE ARE PRODUCED; (F) SUBJECTING THE REMAINING EFFLUX FROM STEP (B) NOT UTILIZED IN STEP (C) AND THE ORGANIC PHASE FOR STEP (E) TO SULFONATION; (G) NEUTRALIZING OF SULFONATION PRODUCTS FROM STEP (F) BY ADDITION OF AN ALKALINE BASE SELECTED FROM THE GROUP CONSISTING OF ALKALI METAL HYDROXIDES AND AMMONIA; (H) HYDROLYZING THE PRODUCTS THUS NEUTRALIZED WITH AN ALKALINE BASE SELECTED FROM THE GROUP CONSISTING OF ALKALI METAL HYDROXIDES AND AMMONIA, TO CONVERYT SULTONES PRESENT IN THE PRODUCTS TO SULFONATES; (I) RECYCLING TO THE DEHYDROGENATION STEP THE ORGANIC PHASE WHICH CONSISTS OF NORMAL PARAFFINS, AND THE SMALL QUANTITIES OF NAPHTHENE, OLEFIN, AND AROMATIC HYDROCARBONS OBTAINED BY SETTLING AAFTER THE HYDROLYZIN STEP.

Oct. 22, 1974 c, MARTY ETAL DETERGENT COMPOSITIONS AND METHODS OFOBTAINING THEM Filed Feb. 16, 1971 mm mm mm .om fi mm -N a 8 A t v. E 2J x v m 9 Q United States Patent O "ice 3,843,564 DETERGENT COMPOSITIONSAND METHODS OF OBTAINING THEM Claude Marty, Le Havre, Jean Maurin,Montivilliers, and Joseph Edouard Weisang, Le Havre, France, assignorsto Compagnie Francais de Rafiinage, Seine, France Filed Feb. 16, 1971,Ser. No. 115,488 Claims priority, application France, Feb. 16, 1970,7005438 Int. Cl. C11d 1/14, 1/37, 11/04 US. Cl. 252-552 7 ClaimsABSTRACT OF THE DISCLOSURE A detergent composition with linear sidechains and consequent biodegradability being a mixture of orthodialkylbenzene sulfonates, alkenyl sulfonates, and hydroxy alkyl sulfonateswith unexpectedly desirable foaming characteristics in aqueous solution.Also, alkyl sulfate biodegradable detergent compositions. Processes formanufacturing these compositions from normal paraffinic stock of acertain carbon range.

The present invention relates to biodegradable detergent compositionsand also to economic methods of manufacturing said compositions.

Biodegradability of detergents are becoming a necessity in order toavoid the pollution of waters with by-products which bacteria cannotdestroy.

It is known that the alkyl benzene sulfonates obtained by alkylation ofbenzene by propylene tetramer, followed by sulfonation andneutralization with the use of an alkaline base, constitute gooddetergents. However, their biodegradability properties are poor due tobranching in the hydrocarbon chains.

The alkyl benzene sulfonates having linear side chains undergo much morecomplete biological degradation. Consequently, they are tending toreplace the alkyl benzene sulfonates with branched side chains. Thehydrocarbons used in the preparation of the linear alkyl benzenesulfonates are obtained by catalytic alkylation of benzene by a linearolefin or by a normal monochloroparaffin. However, the cost of theseprocesses is very high, on the one hand, because the cost of thealkylation process proper and, on the other hand, due to the fact thattwo raw materials must be prepared, namely, the benzene and the linearolefin or normal monochloroparaffin.

Furthermore, it is known that the sulfation of linear olefins, followedby neutralization, also leads to good biodegradable detergents which areavailable in the form of concentrated aqueous solutions.

An object of the present invention is to produce high quality detergentcompositions having good ecological properties, includingbiodegradability, starting from a single raw material.

The applicants have found that such compositions can be obtained fromspecific hydrocarbons, namely, by sulfonation and then neutralization,or by sulfation and then neutralization, followed by a sulfonation and aneutralization.

A preferred embodiment of the present invention is a method of obtainingbiodegradable sulfonate detergent compositions by carrying out in astream of hydrogen a nonisomerizing catalytic dehydrogenation of normalparafiins having between 14 and 24 carbon atoms, eliminating thehydrogen and the cracking products of the said normal parafiins from theeffiux, subjecting the olefin and aromatic hydrocarbons, resulting fromthe dehydrogenation, to a sulfonation by sulfuric anhydride in gaseousstate, and neutralizing and hydrolyzing with an alkaline base theproducts resulting from the sulfonation.

3,843,564 Patented Oct. 22, 1974 Another embodiment of the presentinvention is a similar method for obtaining biodegradable detergentsulfonate and sulfate compositions wherein the olefin and aromatichydrocarbons subjected to the sulfonation are at least in part composedof the hydrocarbons remaining after a sulfation by concentrated sulfuricacid of at least a part of the olefin hydrocarbons resulting from thedehydrogenation of the normal paraffins and by the fact that theproducts resulting from the sulfation are neutralized and hydrolyzed byan alkaline base.

Still another preferred embodiment of the present invention is abiodegradable detergent composition containing, as active products,primarily orthodialkyl benzene sulfonates, alkenyl sulfonates andhydroxy alkyl sulfonates of an alkali metal or ammonium ion. The alkyland alkenyl radicals are linear and contain between 1 and 18 carbonatoms in the case of the ortho-dialkyl benzene sulfonates and between 14and 24 carbon atoms in the case of the alkenyl sulfonates and thehydroxy alkyl sulfonates.

A surprising advantage of the foregoing composition has been discoveredby the applicants; namely, the foam generated by this composition inaqueous solution has unexpectedly a desirable degree of stability. Thisproperty is not one which would be deduced from the correspondingproperties of the individual components of the composition. It is knownthat the foam produced by detergent compositions must have a certaindegree of stability. However, ecologically it is important that thedetergent composition foam not be too stable. Such foam discharged withwaste water into the public waterways must not remain floating on thesurface of the water for long dis tances, or it will result in adisagreeable accumulation of scum. Instead, it should rapidly dispersethe detergent of the foam into the waste water.

The alkyl aryl sulfonates have satisfactory foam stability. However,because alkenyl sulfonates and hydroxyalkyl sulfonates produce foams ofsuch quantity and stability, it is usual to include with them additivesadapted to break the foam.

One would suppose, therefore, that the mixture of the particularingredients of the foregoing compositions would give rise to a much toostable foam, especially when (as in the case in Example 11, below) thequantities of alkenyl sulfonates and of hydroxyalkyl sulfonates presentin the composition are clearly in excess of the quantity of the alkylaryl sulfonates. However, tests by the applicants have proven quite thecontrary. Even in this unfavorable case, the detergent composition ofthe present invention, contrary to all expectations, gives rise to afoam having perfectly satisfactory stability, comparable to that ofalkyl aryl sulfonates alone.

Still another embodiment of the present invention 1ncludes biodegradabledetergent compositions containing active products which are primarilyalkyl sulfates of an alkali metal or ammonium ion, the alkyl radicalsbeing linear and containing between 14 and 24 carbon atoms.

In the method of the invention, the charge of normal paraffin which issubjected to the dehydrogenation can be prepared by various methods.Thus a fraction rich in normal parafiins can be subjected to anextractive crystallization in urea or to a selective absorption onmolecular sieves. These two methods are known and will, therefore, notbe described in detail. It is not nemssary to prepare a normal paraffinhaving a specific number of carbon atoms between 14 and 24; theinvention may, as a matter of fact, be carried out on a mixture ofhydrocarbons. Extractive crystallization with urea is, however, themethod preferred by the applicants. The preferred fraction is that whichconsists of normal paraffins having between 15 and 21 carbon'atoms.

The catalytic dehydrogenation of normal paraifins is carried out in thepresence of hydrogen under pressure. This gas is introduced with thecharge. The hydrogen can be recovered in the elflux and be recycled tothe dehydrogenation reactor. The composition of the catalyst used is notcritical, and this constitutes one of the advantages of the process. Onesuch catalyst consists of metals having dehydrogenating propertiesdeposited on a support, such as alumina. However, it is necessary thatthe catalyst is not isomerizing, and in order to obtain this property,the acid sites of the support, should the latter contain any, areneutralized for this purpose. It is advantageous to employ a catalystconsisting of chromium oxide and potassium oxide deposited on alumina.Mention may also be made of the catalyst consisting of platinum,lithium, and arsenic deposited on alumina. The conditions under whichthe dehydrogenation is effected depend on the catalyst used. Thetemperature is generally between 250 C. and 500 C. The rate ofconversion of the normal parafiins can be substantial. As a matter offact, the method of the invention does not make it necessary to obtainsolely olefin hydro carbons.

The efilux of the dehydrogenation reactor is formed of hydrogen,unreacted normal paraffins and aromatic and olefin hydrocarbons, as wellas traces of naphthenes and cracking products. After separation of thehydrogen, it is advantageous to eliminate the cracking products fromthis effiux. This can be effected in simple fashion by distillation.

A distinctive characteristic of the invention resides in the fact thatthe aromatic and olefin hydrocarbons coming from the dehydrogenation ofthe normal paraflins are subjected simultaneously to a sulfonationreaction or to a sulfation reaction followed by a sulfouation reaction.These reactions may be effected either on the mixture of unreactednormal paraffins, ole-fin and aromatic hydrocarbons and naphthenes, oron a mixture containing only olefin and aromatic hydrocarbons.

In a first embodiment of the process of the invention, thedehydrogenation efilux after removal of the hydrogen and the crackingproducts is subjected to a sulfonation in a reactor at room temperatureby gaseous sulfuric anhydride, diluted in a gas, which latter does notreact with the products of the reaction under the operating conditions(this is true of nitrogen and air). The sulfonation is effected, forinstance, by causing the sulfuric anhydride to sweep over a thin film ofhydrocarbons or by bubbling sulfuric anhydride into the liquid mass ofhydrocarbons.

After sulfonation, the resultant products 'are subjected toneutralization by soda at ordinary temperature. Thereupon, by analkaline hydrolysis in an autoclave by means of excess soda, at atemperature between 150 C. and 260 C., the sultones are transformed intosulfonates. By settling, there is obtained an aqueous phase containingthe sodium sulfonates and an organic phase which contains primarily thenormal paraffins which did not react upon the dehydrogenation and smallquantities of naphthenes and olefin and aromatic hydrocarbons. Thisorganic phase is recycled to the dehydrogenation reactor.

A second embodiment of the method of the invention consists in sulfatingthe efllux of the dehydrogenation reactor, which has been freed of thehydrogen and cracking products, by contact with sulfuric acid of aconcentration 1 of more than 90 percent at room temperature or lower forshort periods of contact, and then neutralizing the resultant productswith soda at room temperature and effecting an alkaline hydrolysis withsoda at the temperature of 80 C., preferably on the organic phaseobtained 4 of recovering the hydrocarbons to be recycled; they simplyseparate out after the alkaline hydrolysis.

The third and fourth embodiments of the invention are similar to thefirst and second embodiments, respectively; however, the chargesubjected to the sulfonation or sulfation is previously treated so as toremove the normal paraffins and the traces of naphthenes which arerecycled to the dehydrogenation reactor. This separation can be effectedby selective absorption on molecular sieves. The volume of the organicphase collected after hydrolysis of the sulfonates is much less thanthat obtained with the first and second embodiments of the invention.This volume is recycled to the sulfonation reactor.

The aqueous phase which contains the sulfates, as well as the aqueousphase which contains the sulfonates, may contain traces of hydrocarbons.These traces are extracted by means of a suitable solvent, for instance,a mixture of ether and normal pentane or a mixture of ether, normalpentane and isopropyl alcohol The sodium alkyl sulfates obtained arecolorless liquids. The number of carbon atoms in these sulfates islarger than the number of carbon atoms in the sulfate at presentavailable on the market since the sulfates comprise, in accordance withthe invention and depending on the fraction from which one starts,between 14 and 24 carbon atoms which form a nonbranched chain.

The sodium sul-fonate composition obtained consists of a mixture ofortho-dialkyl benzene sulfonates, alkenyl sulfonates and hydroxy alkylsulfonates.

After effecting the evaporation of the water, the sulfonates areobtained in the form of a powder. This phase may be carried out in aspray tower into which the solution of sulfonates are introduced againsta counter-current of hot air. Furthermore, this apparatus has theadvantage of effecting the removal of oil.

When it is desired to obtain a completely colorless powder, it may beadvantageous to effect the decoloration of the sulfonates with the useof a dilute solution of sodium hypochlorite; however, this treatment isnot necessary and, furthermore, has no effect on the detergentproperties of the composition.

Reference is made to the applicants earlier copending application, Ser.No. 22,337, filed Mar. 24, 1970, now Pat. No. 3,761,532 for priority ofany common subject matter claimed herein and otherwise for generalizedbackground of the improvement.

The sole figure attached to the specification is a diagram of apreferred process of the invention. It is not intended to be limitative.Referring to said figure:

A gas oil rich in normal paratfins and having between 15 and 21 carbonatoms is introduced through the line 1 into a urea selective extractionunit 2. This unit 2 has not been shown in detail in the figure. Thedewaxed gas oil is collected via the line 3a. The normal parafiins arein-. troduced into a nonisomerizing dehydrogenation reactor 6 via theline 3, the recycled hydrocarbons (which are composed primarily ofnormal parafiins and traces of naphthenes) via the line 4, and thehydrogen via the line 5. The dehydrogenation catalyst consists ofplatinum, lithium, and arsenic deposited on an alumina support inquantities, expressed in percent of the weight of the catalyst, of0.75,.0.50, and 0.36, respectivelyfThe hourly space speed of the liquidcharge is equal to l. The molar ratio of hydrogen to hydrocarbons isequal to 5. The operation is carried out at a temperature of 450 C., thepressure being slightly more than 1 bar. V After separation of thehydrogen at 7, a part thereof is recycled via the line 5, while thecracking products composed primarily of hydrocarbons having a number ofcarbon atoms of between 6 and 15 are removed at the top of a column 8and evacuated through the line 9. I

A part of the distillation residue is introduced through the line 10into a sulfation reactor 11. The sulfuric acid of a concentration of 98percent is introduced into the reactor through the line 12. The time ofcontact between the sulfuric acid and the charge is 5 minutes. Thetemperature of the reactor is fixed at 5 C. .The effiux is thenintroduced into a neutralization reactor 13 into which soda of aconcentration of 4 N is introduced through the line 14. Theneutralization is effected at room temperature. The efllux is thensubjected to alkaline hydrolysis in the reactor 15 for a period of threehours at a temperature of 80 C.

After decantation in the container 16, the sodium alkyl sulfates arerecovered via the line 17. They can be subjected to a de-oiling, whichhas not been shown in the diagram. The organic phase discharged throughthe line 18 from the decantation vessel, as well as the distillationresidue coming from the column 8 which circulates in the line 19, areintroduced into a sulfonation reactor 20. A stream ofnitrogen,'containing 1 percent by weight sulfuric anhydride in gaseousform, is introduced into the liquid mass of the hydrocarbons via theline 21. The efilux from the sulfonation reactor is introduced into aneutralization reactor 23 into which soda of a concentration of 4 N isintroduced through the line 24. The neutralization is effected at roomtemperature. An alkaline hydrolysis of the efflux is then effected inthe reactor 25 at 250 C. for 1 hour under a pressure of 41 bars. Afterdecantation in the vessel 26, the organic phase, composed primarily ofnormal paraffins which have not been reacted in the reactor 6, togetherwith traces of naphthenes, is recycled via the line 4. The aqueous phaseis introduced via the line 27 into a de-oiling' device 28. The solvent,composed of a mixture of ethyl ether and normal pentane, is introducedthrough the line 29. After decantation in the vessel 30, the organicphase, consisting of the traces of oil dissolved in the solvent, isrecovered via the line 31 and a solution of the sulfonates via the line32. The latter are introduced into an evaporation device 33 from wherethe powder of the sulfonates is collected by the line 34, the waterbeing eliminated through the line 35.

A variant of the embodiment of the method described in the diagramconsists in placing a settling vessel between the neutralization reactor13 and the hydrolysis reactor 15. There is thus recovered an aqueousphase which is is composed of sulfates and an organic phase which issubjected to hydrolysis in the reactor 15. After hydrolysis of thesulfuric diesters, an aqueous phase 17, consisting of sulfates, and anorganic phase 18 are collected in the settling vessel 16, the organicphase being subjected to sulfonation. v i

The invention is further illustrated by the following examples which arenot of a .limitative character.

EXAMPLEI Temperature: 440 C. Hourly space velocity of the liquidmoctadecane: 1 Molar ratio .of hydrogen to normal octadecane: 5.

In Table I below there is found the conversion of the normal octadecane,the yields of ,the .components ofthe efllux and the isomeri zationratefor ,100 g. of converted charge, as well as the composition of thearomatic hydrocarbons expressed in weight for 100 g. of aromatichydrocarbons.

6 TABLE I Conversion, percent 31 Yield (in grams per 100 g. of convertedproduct):

Hydrogen 2.1 Cracked products:

Gaseous hydrocarbons+(number of carbon atoms 5) 1.7 Liquid hydrocarbons(number of carbon atoms )5) 5.9 Olefin hydrocarbons 41.0 Aromatichydrocarbons 44.3 Naphthene hydrocarbons 40 Carbon 1.0 Isomerizationrate 2.0

Analysis by mass spectrometry of the aromatic hydrocarbons obtainedreveals that they are composed primarily of dialkyl benzenes. By nuclearmagnetic resonance the applicants have found that they are orthodialkylbenzenes having linear alkyl radicals.

This table shows that one can expect relatively high conversion rates.Furthermore, it is noted that the isomerization rate, as well as thequantities of cracked products, are very low. The olefin hydrocarbonsobtained consist of more than percent monoolefins.

After removal of the hydrogen and the cracked products, the effiux fromthe dehydrogenation reactor is subjected to sulfation at a temperatureof 5 C. by means of 98 percent sulfuric acid. The contact time is short(5 minutes) so as to avoid the formation of polymers. The molar ratio ofsulfuric acid to olefins to be sulfated is equal to 1.5.

The conversion rate of the olefin hydrocarbons (which are the only onesones to react with the sulfuric acid) is equal to 52 percent, includingless than 5 percent polymers. The total yield of sodium alkyl sulfatesper 100 g. of olefins converted is equal to 75 percent (afterneutralization of the sulfuric monoester with 4 N soda at roomtemperature and hydrolysis of the sulfuric diester by a 4 N sodasolution in excess for 3 hours). The aqueous phase obtained is composedprimarily of a solution of sodium alkyl surfates, the alkyl radicalbeing linear and having 18 carbon atoms.

The organic phase is subjected to a sulfonation reaction. A gaseousstream containing 1.2 percent sulfuric anhydride in nitrogen is bubbledinto the said organic phase at a temperature of 22 C. The time ofreaction is 1 /2 hours. The sulfonic acids obtained are then neutralizedwith 4 N soda at room temperature.

An akaline hydrolysis is then effected in an autoclave by means of sodasolution at a temperature of 250 C. for 1 hour. After settling, theorganic phase, which contains the normal octadecane which has not beenconverted as well as the naphthenes, can be recycled into thedehydrogenation reactor. The aqueous phase is composed primarily ofsodium alkenyl sulfonates, sodium hydroxy alkyl sulfonates and sodiumortho-dialkyl benzene sulfonates. The total conversion of the olefin andaromatic hydrocarbons after sulfonation, neutralization and hydrolysisis equal to 96 percent; The aqueous phase can be subjected to ade-oiling in order to extract therefrom the traces of dissolvedhydrocarbons. This extraction can be effected by means of a mixture ofethyl ether and normal pentane. The dehydration yields a biodegradabledetergent powder. This powder contains dissodium sulfate formed upon theneutralization with the soda. The latter may be separated. However, itis not necessary to do so, since sodium sulfate is a substance which iscontained in the composition of wash powders.

EXAMPLE II mina. These three metals have been deposited in the form ofnitrates in such a manner that after calcination at 800 0., they havethe following weight percent composition, referred to the alumina: 4.97%chromium, 3.03% copper, and 1.00% potassium. The hourly space velocityof the normal octadecane measured in liquid state is equal to l; thetemperature of the catalyst is 440 C. The molar ratio of hydrogen tonormal octadecane is equal to 5. The conversion of the normal octadecaneintroduced into the nonisomerizing dehydrogenation reactor is equal to19 percent. For 100 g. of normal octadecane charged, there are collected12.8 g. of olefin hydrocarbons and 5.9 g. of aromatic hydrocarbons. Theolefin hydrocarbons, as well as the aromatic hydrocarbons collected, aresubjected simultaneously to sulfonation by bubbling a gaseous stream ofsulfuric anyhdride in nitrogen, the molar concentration of sulfuricanhydride in nitrogen being equal to 1 percent. After neutralization ofthe sulfonic acids by 4 N soda at ordinary temperature and then alkalinehydrolysis at a temperature of 250 C. and under a pressure of 41 barsfor a period of 1 hour, the excess soda is neutralized by sulfuric acid.Evaporation is effected until a dry product is obtained.

The detergent properties of the product obtained have been compared withthose of an ordinary commercial soap by carrying out the following test.

A wash powder of the following composition was prepar-ed with theproduct of the invention:

Two aqueous solutions were prepared with this powder, one of 5 g./l. ofpure detergent and the other of 2 g./l.

With each solution a cloth, impregnated with a standard soilage (clothmarketed under the name Cotton Soil ClothSl S 47), was washed in theapparatus known by the name of Launderometer under the followingconditions: washing of a sample of 5 g. of cloth in 2 liters of solutionfor 30 minutes at 90 C. with agitation by balls of stainless steel ofabout 6 mm. in diameter.

In order to establish the detergent power, reflection measurements werecarried out with the use of the apparatus sold under the name Photovoltby the Photovolt Corporation.

Ye: luminance of the cloth after washing.

Ys: luminance of the cloth impregnated with the standard soilage.

Yt: luminance of the support cloth not impregnated with the standardsoilage.

The detergent power DP in percent was calculated by means of thefollowing formula:

Under the same conditions, washings of the same cloth were also etfectedwith solutions of 5 g. per liter and 2 g./l. of a current commercialsoap also containing 1 g./l. of anhydrous sodium carbonate. The resultsare set forth in Table II.

Sulfonates prepared in accordance with the method described in Example11 are subjected to the following biodegradability test:

For 7 days a microorganism culture is maintained with constant aerationat a temperature of 25 C. in a semisynthetic medium containing 20 mg.per mil of the product to be tested and then, at the end of this time,the same quantity of detergent is again introduced, and the test iscontinued until the second day. On. the 7th and 10th days determinationsare made to note the elimination of the products and establish theirbiodegradability.

The culture broth used in the tests comprises between 2 and 4x10microorganisms per mm. It was prepared by aerobic fermentation, in arich nutrient medium, of microorganisms taken from the water of theSeine River at the point of discharge of the large Clic'hy sewer inParis.

The detergent content of the microorganism cultures is determined inaccordance with the method of Longwell and Manisoe, the principle ofwhich is as follows: a colored complex is formed with methylene blue; itis extracted with chloroform and a calorimetric measure is effected bycomparison with a standard'product.

The biodegradation rate T at the end of 7 days is given by the formula:

2o- (Cm-0.7) X 100 20 in which C is the content of detergent in the testmedium on the 7th day, expressed in mg. per mil, and Ct is the contentof detergent in a control medium on the 7th day, expressed in mg. permil.

In similar fashion, the biodegradation at the end of 10 days, T is givenby the formula:

The results obtained appear in Table HI below- TABLE III Composition ofthe invention Test Test Control No. 1 No. 2

Concentration of detergent 7th day (parts i 7 per million 0.80 3. 00 '2.30 Biodegradation percent, 7th day 89. 00 92. 50 Concentration ofdetergent, 10th day- 0. 65 p 2. 2. 65 Biodegradation percent, 10th day94. 5 95. 00

Biodegradabilitmln ni 92.6 94.1

Average 93.35

Hydroxyalkyl sulfonates 47 Other 1 2 Total 10 In the commercialproduction the percentage composition for each will range from to 60%for alkyl aryl sulfonates, 8% to 45% for alkenyl sulfonates, and 20% to72% for hydroxyalkyl sulfonates.

We claim:

1. A method for producing alkyl sulfates and mixtures of olefinicsnlfonates and also orthodialkyl benzene sulfonates having detergent andbiodegradable properties with superior foam stability, which methodcomprises the steps of:

(a) Treating normal paraffin hydrocarbons having between 14 and 24carbon atoms with a cyclicizing nonisomerizing dehydrogenation catalystchosen from the group consisting of: chromium oxide and potassium oxide,deposited on alumina; platinum, lithium and arsenic deposited onalumina; and copper, potassium, and chromium deposited on alumina; inthe presence of hydrogen to yield a substantial amount of olefins andsaturated straight chain orthodialkyl benzene hydrocarbons;

(b) Separating hydrogen and cracking products of the saidnormal'parafiin hydrocarbons from the efllux;

(c) Sulfating at least a part of the olefin hydrocarbons resulting fromthe dehydrogenation of the normal parafiin hydrocarbons by contact ofthe said olefins with sulfuric acid of a concentration of more than 90percent for a period of time between 1 and 10 minutes, at a temperaturebelow 25 C.;

(d) Neutralizing the efiluent of the sulfating step by addition of analkaline base selected from the group consisting of alkali metalhydroxides and ammonia;

(e) Hydrolyzing the products thus neutralized with an alkaline baseselected from the group consisting of alkali metal hydroxides andammonia to convert sulfuric esters present in the products from theproducts from the sulfating step to sulfates wherein an organic phaseand an aqueous phase are produced;

(f) Subjecting the remaining efilux from step (b) not utilized in step(c) and the organic phase from step (e) to sulfonation;

(g) Neutralizing the sulfonation products from step (f) by addition ofan alkaline base selected from the group consisting of alkali metalhydroxides and ammonia;

(h) Hydrolyzing the products thus neutralized with an alkaline baseselected from the group consisting of alkali metal hydroxides andammonia, to convert sultones present in the products to sulfonates;

(i) Recycling to the dehydrogenation step the organic phase whichconsists of normal parafiins, and the small quantities of naphthene,olefin, and aromatic hydrocarbons obtained by settling after thehydrolyzing step.

2. A method for producing alkyl sulfates and mixtures of olefinicsulfonates and also orthodialkyl benzene sulfonates having detergent andbiodegradable properties With superior foam stability, which methodcomprises the steps of:

(a) Treating normal parafiin hydrocarbons having between 14 and 24carbon atoms with a cyclizing nonisomerizing dehydrogenation catalystchosen from the group consisting of: chromium oxide and potassium oxide,deposited on alumina; platinum, lithium and arsenic deposited onalumina; and copper, potassium, and chromium deposited on alumina; inthe presence of hydrogen to yield a substantial amount of olefins andsaturated straight chain orthodialkyl benzene hydrocarbons;

(b) Separating out hydrogen and cracking products of said normalparaflin hydrocarbons from the efllux and additionally separatingnaphthene and unreact d parafiin hydrocarbons from said efilux andrecycling the nephthene and unreacted parafiin hydrocarbons to saiddehydrogenation step (a);

(c) Sulfating at least a part of the olefin hydrocarbons resulting fromthe dehydrogenation of the normal paraffin hydrocarbons by contact ofthe said olefins with sulfuric acid of a concentration of more thanpercent for a period of time of between 1 and 10 minutes, at atemperature below 25 C.;

(d) Neutralizing the eflluent of sulfating step by addition of analkaline base selected from the group consisting of alkali metalhydroxides and ammonia;

(e) Hydrolyzing the products thus neutralized with an alkaline baseselected from the group consisting of alkali metal hydroxide and ammoniato convert sulfuric esters present in the products from the sulfatingstep to sulfates, wherein an organic phase and an aqueous phase areproduced;

(f) Subjecting the remaining efllux from step (b) not utilized in step(c) and the organic phase from step (e) to sulfonation;

(g) Neutralizing the sulfonation products from step (if) by addition ofan alkaline base selected from the group consisting of alkali metalhydroxides and ammonia;

(h) Hydrolyzing the products thus neutralized with an alkaline baseselected from the group consisting of alkali metal hydroxides andammonia, at a sufficient temperature above room temperature to convertsultones present in the products to sulfonates;

(i) Recycling the organic phase resulting from the products of thehydrolysis step (h) to the sulfonation step (f):

3. A method as claimed in Claim 2 wherein the separation of thenaphthenes and 14 to 24 carbon normal paraffin hydrocarbons is byselective absorption on molecular sieves.

4. A method as claimed in Claim 1 wherein said neutralizing step (g) isaround room temperature and said hydrolyzing step (h) is at atemperature between C. and 300 C.

5. A method as claimed in Claim 1 wherein said normal paraflins containfrom 15 to 21 carbon atoms.

6. The method of Claim 1 wherein said catalyst consists essentially ofchromium, copper and potassium deposited on alumina in the form ofnitrates and thereafter calcinated to give approximate weightpercentages of 4.99% chromium, 3.03% copper, and 1.00% potas- .sium; thehourly space velocity of the hydrocarbon reactants in said catalyticreaction in step (a) is about one; the temperature of the catalyticreaction in step (a) is about 440 C.; hydrogen is supplied to thereaction in step (a) in a molar ratio relative to said hydrocarbonreactants of about five; and the pressure is about one bar.

7. The method of Claim 1 wherein said catalyst consists essentially ofplatinum, lithium, and arsenic deposited on alumina in amountsapproximately equal to 0.75%, 0.50%, and 0.36%, respectively, of theweight of the catalyst; the hourly space velocity of the hydrocarbonreac tants in said catalytic reaction in step (a) is about one; thetemperature of the catalytic reaction in step (a) is about 440 C.;hydrogen is supplied to the reaction in step (a) in a molar ratiorelative to said hydrocarbon reactants of about five; and the pressureis about one bar.

References Cited UNITED STATES PATENTS 3,506,580 4/1970 Rubinfeld et al.252-550 (XR) 3,458,447 7/1969 Shultz 260-505 A (XR) 3,480,556 11/1969DeWitt et al. 260-458 (XR) 3,437,585 4/ 1969 Kuchar 208-96 3,409,63711/1968 Eccles et al. 260-327 3,346,505 10/1967 'Blakeway et a1. 2525582,210,316 8/1940 Dreisbach 260460 2,871,254 1/1959 Hoog et al. 2604603,531,544 9/1970 Berg 260-6833 (Other references on following page)UNITED STATES PATENTS Taylor et a1. 260-668 Bloch 260-683.3 Keblys260683.3 Kuchar 260--683.3 Kirschenbaum 260-683.3 Eccles et a1. 252558Bloch 260505 A Bloch et a1 260460 FOREIGN PATENTS 8/ 1961 Great Britain.

Great Britain.

I 12 OTHER REFERENCES Liddicoet, Alpha-Olefins in the SurfactantIndustry, IAOCS, vol. 40, November 196-3, pp. 631-633.

5 LEON D. ROSDOL, Primary Examiner P. E. WILLIS, Assistant Examiner[1.8. CI. X.R.

1. A METHOD FOR PRODUCING ALKYL SULFATES AND MIXTURES OF OLEFINICSULFONATES AND ALSO ORTHODIALKYL BENZENE SULFONATES HAVING DETERGENT ANDDIODEGRADABLE PROPERTIES WITH SUPERIOR FOAM STABILITY, WHICH METHODCOMPRISES THE STEPS OF: (A) TREATING NORMAL PARAFFIN HYDROCARBONS HAVINGBETWEEN 14 AND 24 CARBONATION CATALYST CHOSEN FROM ISOMERIZINGDEHYDROGENATION CATALYST CHOSEN FROM THE GROUP CONSISTING OF: CHROMIUMOXIDE AND POTASSIUM OXIDE, DEPOSITED ON ALUMINA; PLATINUM, LITHIUM ANDARSENIC DEPOSITED ON ALUMINA; AND COPPER, POTASSIUM, AND CHROMIUMDEPOSITED ON ALUMINA; IN THE PRESENCE OF HYDROGEN TO YIELD A SUBSTANTIALAMOUNT OF OLEFINS AND SATURATED STRAIGHT CHAIN ORTHODIALKYL BENZENEHYDROCARBONS; (B) SEPARATING HYDROGEN AND CRACKING PRODUCTS OF THE SAIDNORMAL PARAFFIN HYDROCARBONS FROM THE EFFLUX; (C) SULFATING AT LEAST APART OF THE OLEFIN HYDROCARBONS RESULTING FROM THE DEHYDROGENATION OFTHE NORMAL PARAFFIN HYDROCARBONS BY CONTACT OF THE SAID OLEFIN WITHSULFURIC ACID OF A CONCENTRATION OF MORE THAN 90 PERCENT FOR A PERIOD OFTIME BETWEEN 1 AND 10 MINUTES, AT A TEMPERATURE BELOW 25*C.; (D)NEUTRALIZING THE EFFLUENT OF THE SULFATING STEP BY ADDITION OF ANALKALINE BASE SELECTED FROM THE GROUP CONSISTING OF ALKALI METLHYDROXIDES AND AMMONIA (E) HYDROLYZING THE PRODUCTS THUS NEUTRALIZEDWITH AN ALKALINE BASE SELECTED FROM THE GROUP CONSISTING OF ALKALI METALHYDROXIDES AND AMMONIA TO CONVERT SULFURIC ESTERS PRESENT IN THEPRODUCTS FROM THE PRODUCTS FROM THE SULFATING STEP TO SULFATES WHEREINAN ORGANIC PHASE AND AN AQUEOUS PHASE ARE PRODUCED; (F) SUBJECTING THEREMAINING EFFLUX FROM STEP (B) NOT UTILIZED IN STEP (C) AND THE ORGANICPHASE FOR STEP (E) TO SULFONATION; (G) NEUTRALIZING OF SULFONATIONPRODUCTS FROM STEP (F) BY ADDITION OF AN ALKALINE BASE SELECTED FROM THEGROUP CONSISTING OF ALKALI METAL HYDROXIDES AND AMMONIA; (H) HYDROLYZINGTHE PRODUCTS THUS NEUTRALIZED WITH AN ALKALINE BASE SELECTED FROM THEGROUP CONSISTING OF ALKALI METAL HYDROXIDES AND AMMONIA, TO CONVERYTSULTONES PRESENT IN THE PRODUCTS TO SULFONATES; (I) RECYCLING TO THEDEHYDROGENATION STEP THE ORGANIC PHASE WHICH CONSISTS OF NORMALPARAFFINS, AND THE SMALL QUANTITIES OF NAPHTHENE, OLEFIN, AND AROMATICHYDROCARBONS OBTAINED BY SETTLING AAFTER THE HYDROLYZIN STEP.